Manufacture of mirrors



Patented Apr. 1 2, I I v a UNITED ST TES PATENT yorncs Albert Moore Barnes, Acton, London. England, assigner to Duro-Ray Limited; London, England,

a British company a NoDrawing. Application January 23, 1935, Se-

iisghNo. 3,143. Inqreat'Britain February 8,

10 Claims. (cl. 91-091) This invention concerns improvements in the changing temperature, must sooner or later gain manufacture of mirrors of glass or similar transaccess to the perforate silver film and depreciate [parent or translucent materials, particularly or destroy its light reflecting value by oxidation mirrors for domestic and/or decorative purposes. and corrosion. Furthermore, from the imperfect It is common practice in glass silvering to make and partially crystalline perforate structure of 5 use of the well known silver ammonium tartrate the film there is every likelihood of the film, process in any one of its numerous modifications with its backing, stripping from the glass surface in order to produce the silver film itself, and furowing to the lack of that intimate adhesion which ther to back" or protect the silver film thereby is the property of silver solely in the colloidal formed by means of paints and varnishes which state. The loss of light reflecting value caused 10 may, if desired, contain such metals as aluminium by imperfections and extreme tenuity of silver in finely divided particle form, or by electro-p films applied by thev silver ammonium tartrate depositing an extremely thin coating of copper processes is considerable and is commonly as much on to the silver film, the thus applied copper coatas even in good quality silvering.

paints or varnishes, or again 'after applyinga coatlarly mi ors or omestic a d/0r decorativeing of varnish to the copper surface to stretch purposes wherein the silver films are sufficiently a thin sheet of lead over the varnished copper and dense, homogeneous and molecularly adherent to to press or roll it into good mechanical contact, the glass or similar transparent or translucent or alternatively to electro-deposit lead on-to the of the silver films are at their maximum and copper for its better protection'against injury. wher n the ilve film ar adequately protected None of these prior proposals when carried into ag st tm p a Other r n.

practice are entirely satisfactory for mirrors, chanical abrasi x r me v riat ns in atmo particularly mirrors for domestic and/or decora- D e temperature When d as a etive purposes, the principal reason being. the lack fiector of suitable curvature, against heat from of exact knowledge as to the formation and charlight sources suchas electric light or asacteristics of the silver film itself and itsdeposi- This desideratum is fulfilled in accordance with tion on the glass surfaces. Silver films produced he pr e inv nt n in hi h pr for by the silver ammonium tartrate process. in any silveri g ss similar t p e o t ans- 30 of its numerous modifications, are not only xlucent materials, particularly glass for domestic tremely tenuous but, owing to their imperfect. and/or decorative purp is characterized in structure, partially crystalline and pin-holey, that films of colloidal silver only are formed to are more or less light absorbent and in part, or predetermined linear thicknesses on their surfaces 3 whole, do not adhere to the glass surfaces as to facilitate the electro-deposition of metals for intimately as they should. Thus, the silver films P t t ve p p The pp at on of this or deposits, instead of being pure silver in the process to the manufacture of mirrors particularly colloidal state and as such devoid of structure and for d m st and/0r d tive purp ses c nsists in molecular contact with, and positively adn eleetre-depesiting a coating of l p the 40 herent to the glass surfaces, are more or less mixsilver film. 40

tures of silver partly colloidal, but mainly crys- The conditions which should preferab y be obtalline and further contaminated with silver in served in depositing the silver film and in electroother states such as silver oxide. All or any of ep t the metal backing p the ver fi m the structural defects referred to above are likely will now be referred to.

to become more pronounced during and after the The s er Solutions Which. for convenience. 5

application of the various protective paint or other may be d si n ed 8-1. and S2. lor the silver solubackings. For example, granted the structural tions, and R- fer t e uc solution. y be defects referred to above, it is impracticable to considered to resemble those used in the well close or cover up these defects by the chemical or known Brashier process for optical silvering.

5i electro-depositlon of copper because the copper For instance the S.1.solution maybe compounded surface must possess the same structure as that by adding suflicient ammonium hydrate (NHiOH) of the silver film on to which it has been deposited to silver nitrate (AgNOa) dissolved in distilled and When a paint or varnish s su equently apwater to convert the silver nitrate to silver oxide plied as Otecuve s decommsmon and to re-dissolve the precipitated silver oxide in uets Of e. under conditions of moisture and an excess of ammonium hydrate. The 3.2.

ing being further protected by the application of I is a desideratum to Provide mirrors D l6 the lead providingthe metal protective backing, surfaces, wherein the light reflecting properties 20 solution may consist of sodium hydrate (NaO H) dissolved in distilled water. Solution S2. is then added to solution 3.1. and to the mixed 8.2. and 8.1. sufiicient ammonium hydrate is added to redissoive any excess of silver oxide that may appear as a precipitate after adding to 8.1., care being taken to avoid an excess oi. ammonium hydrate. The mixed 8.1. and 8.2. solutions are then diluted with distilled water to a point when the original silver nitrate content is approximately 5.00 grams per litre, and the original sodium hy-' drate content is approximately 4.68 grams per litre; The R. solution may consist of cane sughr and tartaric acid dissolved in sufiicient distilled water and in such proportion that it contains cane sugar 4.00 grams per litre and tartaric acid 0.24 gram per litre. The solutions 8.1. and 5.2. and the solution R. are purposely so compounded that equal volumes of solutions 8.1. and 8.2. and R. react when issuing from their respective nozzles referred to hereinafter and mix or mingle to form a jet of mixed solution double the volume of the separate solutions, (S.l.+S.2. and R.) and are purposely contrived to procure the exact condition of silver deposit, only in the colloidal state, on the surface of the material under treatment for example glass for domestic and/or decorativepurthe work to allow the solutions to be fed to the work by gravity. Alternatively compressed air may be used for this purpose the containing vessels being kept at any convenient level. The solutions for silverings S.1.+S.2. and R. are caused to issue under the control of suitable valves or taps connected with the containers by suitable tubes or ducts. Each individual jet or combination of jets consists of two separate nozzles disposed towards each other at an angle of say 45. Each jet consists of two nozzles, separately connected, one to the solutions S.1.+S.2., the other to the solution R. The solutions issuing from their respective nozzles, disposed towards each other at 45 are caused to mix at a calculated distance clear of the nozzles and by the adjusted volume of the flow of the solutions, they become a single jet of mixed solutions double the volume of the flow of the issue from the separate nozzles. At the point of the mingling of the two solutions, and by their calculated reaction when mixed, the jet or jets of mingled solution become actively silver depositing and when caused to flow over the glass or similar surfaces under treatment deposit pure silver in the colloidal state required, firstly as a slight discoloration or film of silver in the colloidal state. This film is rapidly built up by the constantly renewed flow of the mixed solutions which are only allowed to remain on the surface of the glass or similar transparent or translucent substance for example glass for domesticand/or decorative purposes whilst active in respect of the first calculated reaction and which drain off before depositing silver in other states than the colloidal state required for the purpose in view. The procfilm of silver in the colloidal state, adherent to and apparently'in molecular contact with the glass or similar surface for example glass for domestic and/or decorative purposes, has been formed, the work is transferred to a bath for electro-depositing the lead backing.

This bath should be so constituted that the adhesion of the silver film to the glass is not adversely affected by the acid or alkaline reaction lead to the minimum.

By the calculated composition of the lead-containing electrolyte, the disposition of the lead anodes towards the cathode, (the silver iilm in contact .with the glass or similar surfaces under treatment), and the electric current employed to complete the electro-deposition of the lead backing, a dense, non-crystalline and homogeneous coating of pure lead can be deposited on every portion of the outer surface of the silver film in such a manner that it is encased with pure and ductile lead, to such a predetermined thickness as to afford protection againstmechanical injury, sea -air, damp and moisture, and most of the more injurious fumes and gases likely to be encountered. Experience indicates that a lead deposit 0.002 inch in linear thickness is sufiicient for this purpose but this thickness can be varied in either direction by a simple time adjustment.

The apparatus for carrying the process into effect comprises:

1. Means to hold and secure the glass sheet in position during the silvering process and at the same time to impart motion, which may be circular, gyratory or reciprocating in a horizontal plane. Oneway for securing this is to attach a vacuum plate or cup to the underside of the glass sheet and by means of a spindle carrying'a ball which engages with a socket attached to the vacuum. cup to support the glass on a circular table attached to a supporting pedestal in such a manner that it remains level or can be rotated whilst level in a horizontal plane, or can be lifted by its spindle attached to the vacuum cup to a suflicient height above the circular table attached to the supporting pedestal so that resting in an inclined position on the circular table the glass with the vacuum cup attached can be rotated at an angle inclined to the horizontal with a gyratory movement, or in any inclined plane desired, for the purpose of creating the proper flow of the silvering solution over the glass surface during the silvering process.

Alternatively the glass may be mounted on a suitable supporting table, and whilst so supported, by mechanical means such as gimbals or a system of levers and pendulums the table supporting the glass sheet may be inclined at any desired angle to secure the desired flow of solutions over and from the glass surface during the silvering operation. Trays or troughs can be arranged to collect the spent solutions draining from the glass during the silver-mg operation. The silvering,

conducted at normal atmospheric temperaturesuch as 65 F., does not call for the steam heated tables employed in silvering by the silver ammonium 'tartrate process. I

'2. Means for electro-vdepositing pure metallic lead as a protective backing directly on to the silver film previously deposited onto the glass surface as described comprise a suitable tank or vat to. hold the electrolyte, lead anodes properly disposed in relation to the silvered glass sheet to be treated and a supporting frame to carry the silvered glass during the electro-deposition provided with contacts and electrical connections to couple up the silver film, acting now as the cathode in the lead depositing process, to the source of electric supply.

The mirrors produced in accordance with this invention consist primarily of a sheet of plane or curved glass or similar transparent or translucent material, a fihn of pure silver adherent to and in apparent molecular contact with the glass or similar transparent or translucent material and purposely contrived to be sufliciently dense and homogeneous so as to render it totally or 100% light reflecting for the value of pure silver as a light reflecting medium, and secondly of a coating of pure lead incorporated and in positive metallic contact with the underlying silver film. This protective coating of pure lead is homogeneous and imperforate by reason of its,

method of application upon an imperforate silver film produced as hereinbefore described and is calculated to protect permanently the silver film against such corrosive agencies as sea-air, damp and moisture and atmospheric and chemical fumes and gases. Since there is no place in the lead backing where moisture, fumes and gases can attack the silver film, its value, as the most efiicient light reflecting surface obtainable, is permanently unimpaired by oxidation or corrosion from any external or internal source.

What I claim is:

1. A process for the manufacture of mirrors comprising the steps of forming a fllm of colloidal silver only to a predetermined linear thickness on a surface of transparent material and of electro-depositing on the silver film a coating of lead for protective purposes.

2. A process for the manufacture of mirrors comprising the steps of forming a film of colloidal silver only to a predetermined linear thickness on a surface of translucent material and of electrodepositing on the silver film a coating of lead for protective purposes.

3. A process for the manufacture of mirrors comprising the steps of forming a film of colloidal silver only to a predetermined linear thickness on v a surface of glass and of electro-depositing on the silver film a coating of lead for protective purposes.

4. As a new article of manufacture a mirror consisting of transparent material, an adherent film of silver exclusively in the colloidal state upon the surface of said material and a protective backing of electro deposited lead upon the silver film.

5. As a new article of manufacture a mirror consisting of translucent material, an adherent film of silver exclusively in the colloidal state upon the surface of said material and a protective backing of electro-deposited lead upon the silver film.

6. As a new article of manufacture a mirror consisting of glass, an adherent film of silver exclusively in the colloidal state upon the glass and a protective backing of electrodeposited lead upon the silver film.

'7. A process for silvering glass and the like,

comprising subjecting the glass to the action of newly combined component silvering solutions for 'tion for such time as will cause the deposit thereon of only colloidal silver, draining the solution from the glass before silver in other than colloidal form is deposited, repeating such sequence of depositing and draining operations until the colloidal silver deposit on the glass is built up to a desired thickness, and electro-depositing a backing of lead on the colloidal silver deposit.

9. A process for silvering glass and the like, comprising preparing a solution of silver nitrate in water, adding ammonium hydrate to said solution until a precipitate of silver oxide is formed, adding an excess of ammonium hydrate to the solution to dissolve the silver oxide, adding a sov lution of sodium hydrate to said solution, adding ammonium hydrate to the mixture to dissolve any silver oxide formed, mingling a stream of the mixture of solutions with a stream of reducing solution of. cane sugar and tartaric acid in water, immediately flowing said mingled streams of solutions over the glass to be silvered, draining the mixture from the glass before silver in other than colloidal form is deposited, continuing to fiow fresh portions of said solutions, immediately after mingling, oversaid glass until a silver deposit of desired density is obtained, and electro-depositing a layer of lead directly on the silver deposit.

10. A process for silvering glass and the like, comprising preparing a solution of silver nitrate in water, adding ammonium hydrate to said solution until a precipitate of silver oxide is formed, adding an excess of ammonium hydrate to theselution to dissolve the silver oxide, adding a solution of sodium hydrate to said solution, adding ammonium hydrate to the mixture to dissolve any silver oxide formed, said mixed solutions having an original silver nitrate content of approximately 5.00 grams per liter and an original sodium hydrate content of approximately 4.68 grams per liter, mingling a stream of the mixture of solutions with a stream of reducing solution of cane sugar and tartaric acid in water, said reducing solution having a cane sugar content of approximately 4.00 grams per liter and a tartaric acid content of approximately 0.24 gram per liter, immediately flowing said mingled streams of solutions over the glass to be silvered, draining the mixture from the glass before-silver in other than colloidal form is deposited, continuing to. flow fresh portions of said solutions, immediately after mingling, over said-glass for ten to fifteen minutes, and electro-depositing a backing layer of lead on the silver deposit in an electrolyte consisting of an aqueous solution of lead perchlorate in which the lead content is approximately 37.5 gramsper liter and the freeperchloric acid content is approximately 0.05 p

' ALBERT MOORE BARNES. 

